N-alkyl-n-formyl-2-halo-2-alkyl acetamides



United States Patent 6 Claims. (or. 260-561 The present application is a division of copending application, Serial No. 42,751, filed July 14, 1960.

The present invention is concerned with novel intermediates for the preparation of new insecticidal and acaricidal monothiophosphoric and dithiophosphoric acid esters.

The aforesaid new monothiophosphoric and dithiophosphoric acid esters correspond to the formula wherein each of R and R represents CH or C H R stands for methyl, ethyl or propyl, R stands for H, methyl, ethyl or propyl, and Y stands for an oxygen atom or a sulfur atom.

Compounds 1 can advantageously be prepared by reacting a compoundof the formula oflia 1| X-biI-O-N-OHO wherein R and R, have the precedingly-recited significances and X stands for halogen with a compound of the formula PS-Z wherein Y is as precedingly recited and Z is a cation. Where Z is H, the reaction is carried out in the presence of an acid-binding agent.

The reaction is advantageously carried out in a solvent such as acetone, methylethylketone, dioxane or water or in an aliphatic or aromatic hydrocarbon or in a 1nixture .of such solvents, at normal or slightly raised temperature.

Suitable compounds of Formula II are for example the .chloroacetyl-N-alkyhformamides such as chloroacetyLN- mcthyl-formamide, chloroacetyl-N-ethyl-formamide, chloroacetyl-Nisopropyl-formamide, as well as cc-ClllOl"G- propionyl-N-methyl-formamide; also the corresponding bromo compounds. These intermediates are themselves new compounds and the claims of the present application are directed exclusively thereto.

Suitable compounds of Formula III are for example:

etc.

3,232,987 Patented Feb. 1., 1966 The monothiophosphoric and dithiophosphoric acid esters I are liquid at room temperature (about 20 to about 30 C.). They are generally soluble in oils as well as in organic solvents, and are easily emulsifiable in water. The new esters I are outstandingly suitable for combating pests, more especially insects and spider mites (Tetranychidae sp.), in the protection of plants. Some of the compounds I are distinguished by excellent systemic action.

As will hereinafter appear, the new compounds I are distinguished from known systemically acting insecticides by reduced toxicity to warm-blooded animals, while having as good or better systemic action.

-( 1) ORAL TOXICITY-OF ACTIVE SUBSTANCES LDa (ma/ks) Formula of active ingredient of composition- White i mouse Rat titre of the thiono and thiolo forms). (Cl-I3O) PSSCH2CON|--CH CHO (NorE.Compcsiti0ns 1 to 4 are commercial preparations available on the market; composition 5 is according to Example 1 of the present application.)

(2) SYSTEMIC ACTION Potted spiderwort plants are each watered with milliliters of an aqueous emulsion of the insecticide being tested in such manner that the emulsion comes in contact only with the root system of the plants.

On the next day, each plant has applied thereto 30 grasshoppers (Carausius morosus) in the 2nd larval stage. The systemic-insecticidal action of the various insecticides is checked daily by counting the number of dead insects.

The observed results are characterized by indication of the mortality (in percent of the applied insects) after x days after the treatment (percent/ x) In combating pests by means of the new monot-hiophosphoric and diethiophosphoric acid esters of Formula I, the latter are advanageously admixed with emulsifying agents, for example with liquid polyglycol ethers obtained from higher alcohols, mercaptans or alkylphenolsby adding on ethylene oxide, then emulsifying the mixture in water, and applying the emulsion by spraying thereof onto the surfaces to be treated. Solution aids, such as suitable organic solvents, for example monoor poly-alcoho1s, ketones, aromatic hydrocarbons, mineral oils, etc., may be incorporated into the mixtures of ester I and emulsifying agents. In order to produce water-suspendible pulverulent products, there may also be incorporated into the said mixtures, solid carriers such as talc, kaolin, kieselguhr, bentonite, etc. The liquid or pulverulent products are emulsified or dispersed in water before being used, it being preferable that the resultant emulsions or dispersions should contain 0.005 to 0.2% by weight of ester I.

However, the new monothiophosphoric and diethiophosphoric acid esters I can also be used without emulsifiers, in which event the esters are advantageously admixed with adhesion promoting agents and inert carriers, such as talc, kaolin, kieselguhr, bentonite, etc., or with a mixture of such carriers, so that the product may be used as a dusting composition or scattering composition.

The following examples set forth presently preferred exemplary embodiments of the invention. Parts and percentages are by Weight unless otherwise indicated. The relationship of parts by weight to parts by volume is the same as that between grams and milliliters. Temperatures are in degrees centrigrade.

is stirred in dropwise at about 80 in the course of 1 to 2 hours. Stirring of the reaction mixture is then further continued at the said temperature until hydrogen chloride development has practically ceased.

EXAMPLE 1 59 parts(=1 mol) of the compound of the formula CH NHCHO are dissolved in 100 parts by volume of trichloroethylene and the resultant solution is stirred dropwise in the course of 1 to 2 hours into a solution, heated to 80, of 112 parts (=1 mol) of chloroacetic acid chloride in 200 parts 9 by volume of trichloroethylene. Stirring is then continued from about one more hour at 80. The resultant reaction product of the formula 0101120 ON-CHa is recovered from the reaction mixture by distillation. Yield: 85%. Boiling points: 70-71/O.4 mm.,

Found: 26.5%.

EXAMPLE 2 The procedure according to Example 1 is repeated, using-as starting materialschloroacetic acid chloride and the formamide of the formula C H NHCHO The obtained intermediate of the formula ClCHzC ON-C2H5 JHO Cl calc.: 26.2%.

has a boiling point of 6970/0.4 mm., n =1.484O. Cl calc.: 23.7%. Found: 24.2%.

EXAMPLE 3 In analogous manner, from chloroacetic acid chloride and the formamide of the formula iso-C H NI-ICHO there is obtained the intermediate of the formula 0101118 ONCzII1-is0 CHO which has a boiling point of 61-63/0.3 mm., n =1.4482. Cl calc.: 21.7%. Found: 21.1%.

EXAMPLE 4 In similar manner, from chloroacetic acid chloride and the formamide of the formula n-C H NHCO there is obtained the intermediate of the formula ClCH CON-C H n Boiling point: 79-82/ 0.7 mm., n =1.4702.

EXAMPLE 5 In analogous manner, from a-chloropropionic acid chloride CH CHClCOC1 and the formamide of the formula CH NHCHO there is obtained the intermediate of the formula CHaCHClCONOHa which boils at 6467/ 0.5 mm., n =1.4812. Cl calc.:

Found: 23.3%. N calc.: 9.36%. Found: 9.46%.

B. Examples of the preparation and use of the end products of the formula R O\fi' R4 ([3110 IS HCON-Ra R20 EXAMPLE 6 68 parts of the compound of the formula ClCHzCON-CH3 and parts of the compound of the formula are stirred together for 4 hours in 300 parts by volume of chloroform at about 55. The chloroform layer is then Washed successively with water, 5% aqueous sodium bicarbonate solution and again with Water. After drying the chloroform layer and distilling off the chloroform, there is obtained in an about 85% yield the compound of the formula in the form of a yellow oil. n =1.5522. P calc.: 12.0%. Found: 12.1%. S calc.: 24.9%. Found: 25.4%.

EXAMPLE 7 30 parts of the compound of the formula ClCI-IzCON-C2H and 37 parts of the compound of the formula (CH O PSSNH are stirred together for 2 hours in parts by volume of acetone at 50. After the addition of 600 parts by volume of water, the organic layer is extracted with chloroform, the chloroform extract washed successively with water, 5% aqueous sodium bicarbonate solution and again with Water, and then dried. After distilling off the chloroform, there remains as residue in an about 85% yield the compound of the formula 11.4%. Found: 11.6%. S 24.4%.

n =1.5384. P calc.: calc.: 23.6%. Found:

EXAMPLE 8 33 parts of the compound of the formula 0101120 ONCH(CHs)z and 37 parts of the compound of the formula (CI-I 0 PSSNH are stirred together for 4-hours in 200 parts by volume of dioxane at 60. After addition of 1000 parts of volume of Water, the organic layer is extracted with chloroform. After drying the chloroform extract and distilling off the chloroform, there is obtained .in an about 80% yield the compound of the formula I in the form of a yellow-brown oil. P

calc.: 10.9%. Found: 11.2%.

EXAMPLE 9 27 parts of the compound of the formula ClCHzCON-CH:

and 40 parts of the compound of the formula 0 (CzH O)2i SNa are stirred together for 2 hours in 200 parts by volume of acetone at 50. The acetone solution is then cooled and separated from precipitated NaCl by filtration. The acetone is distilled from the filtrate, the residue taken up in ether, the ether solution Washed With water and dried over sodium sulfate.

fter distilling off the ether, there remains as residue in practically quantitative yield the compound of the formula CHO n =1.4928. P calc.: 11.5%. Found: 11.2%. S calc.: 11.9%. Found: 11.7%.

EXAMPLE 41 parts of the compound of the formula (CZH5O)2i S- A and 50 parts of the compound of the formula GHaCHClC ON-OIIa are stirred together for 2 hours in 200 parts by volume of acetone at 50. After the addition of 1000 parts by volume of Water, the organic layer is extracted With chloroform. After drying the extract and distilling off the 6 chloroform, there is obtained in an about 75% yield the compound of the formula H3 (IJHO in the form of a yellowish oil. rz =1.5257. N calc.: 4.7%. Found: 4.9%. F calc.: 10.4%. Found: 10.9%.

Scale: 21.9%. Found: 21.8%.

EXAMPLE 11' In analogous manner (to that of Example 10), there is obtained from the compound of the formula s (cHaOni sNHl and the compound of the formula C113CHCICONCH3 110 the compound of the formula (cIIaO)2i s cH2OoN--OH3 on CBO in the form of a brownish-yellow oil. n =1.531 4. P calc.: 11.4%. Found: 12.1%.- S calc.: 23.6%. Found:

' EXAMPLE 12 parts of the ester of the formula II ornonr s @1120 our-0H;

CHO

are admixed with 50 parts of isooctylphenylheptaglycolether, a clear solution being obtained. An aqueous emul- *sion of this solution, Which emulsion contains 0.02% of the ester, is sprayed on young apple trees infested with aphis. In a few hours, all aphis have been killed.

EXAMPLE 13 20 parts of the ester of the formula are admixed with 20 parts of laurylhexaglycolether and parts of xylene, the resultant product being readily Water-emulsifiable. An aqueous emulsion of this prod not, which emulsion contains 0.2% of the ester, is sprayed on aphis-infested potted plants (cineraria, aster, chrysanthemum). In a short time, all aphis are dead.

EXAMPLE 15 (a) By admixing 25 parts of the ester of the formula ll (CI-IaO)zPSCHzC ON-OHs with 25 parts of diisohexyl-heptylphenylhexaglycolether, 25 parts of Xylene and 25 parts of diethyleneglycol, a product is obtained which is well emulsifiable with water. Potted spiderwort plants of a height of about 20 cm. are each watered with 100 milliliters of an aqueous emulsion of the said product, such emulsion containing 0.02% of the active ester, care being taken that no green parts of the plant are Wetted. The next day, 30 grasshopper larvae (Carausius morosus), second stage, are applied to each plant. The larvae feed on the leaves and in this Way also include in their nourishment the aforesaid active ester which has been taken in by the roots of the plants and transported to the leaves. At the end of 8 days, no living larvae remain; all are dead.

(b) An aqueous emulsion of the same product, containing 0.2% of active ester, is sprayed on aphis-infected plants of Erigeron canadense, in such manner that only the bottom part of the plants (not roots) are contacted, while the upper part of the plantswhere the aphis areremains untreated. After two to three days, all aphis on the not-directly treated upper part are dead.

(c) Bean plants in the two-leaf stage and which are infested with Aphz's fabae are sprayed with an aqueous emulsion of the same composition-0.02% of active esterwhereupon, in a few hours, all the aphis have been killed.

EXAMPLE 16 A pulverulent product of good suspendability in water is obtained by intimately admixing 15 parts of the ester of the formula with 3 parts of tert. dodecylmercaptanundecaglycolether, 7 parts of powdered silica gel and 75 parts of kaolin. A suspension prepared from this mixture and containing 0.1% of the said ester, when sprayed on aphis, produces a complete kill in a few hours.

EXAMPLE 17 2 parts of the ester of the formula (C2H50)2:i. SCHzCON-OI'I3 wherein R is alkyl With at most three carbon atoms, and R is -C,,H wherein n is a numeral from 0 to 3 inclusive.

2. The compound of the formula 3. The compound of the formula olorno ONC2H5 4. The compound of the formula 01o H2CONCII(OH3)2 5. The compound of the formula 0101120 ONC H n 6. The compound of the formula CHsCHClCON-CH3 References Cited by the Examiner Fieser et al.: Organic Chemistry, 2nd ed., pages 216- 17, Boston, Heath, 1950.

Hamm et al.: J our. Ag. and Food Chem, vol. 4, N0. 6, pages 518-522 (1956).

Harries et al.: Berichte, vol. 43, pages 634-39 (1910).

Smirnova et al.: Chemical Abstracts, vol. 47, page 3233 (1953).

WALTER A. MODANCE, Primary Examiner. 

1. A COMPOUND OF THE FORMULA 